Esters of phenylindan used as plasticizers and crosslinking agents

ABSTRACT

The dicarboxyallyl, dicarboxymethallyl and mixed carboxyallyl carboxymethallyl esters of phenyl indan are novel compositions of matter. These compounds are useful as crosslinking and plasticizing agents for polymeric compositions.

United States Patent 1191 Aronoff et al. Oct. 1, 1974 ESTERS OF PHENYLINDAN USED AS [56] Refer nce Cit d PLASTICIZERS AND CROSSLINKING UNITED STATES PATENTS AGENTS 2,780,609 2 1957 Petropoulos 260/475 FR [75] Inventors: Elihu J. Aronoff, Framingham;

Kewal Singh Dhami, Shrewsbury, both of Mass. Primary Examiner-Allan Lieberman Assistant Examiner-Richard Zaitlen [73] Asslgnee r fiigggz g ggligggz :2; York Attorney, Agent, or Firm.l. B. Raden; M. M. Chaban 9 a '21 NY.

[22] Filed: June 22, 1973 57 ABSTRACT [21] Appl. No; 372,834 The dicarboxyallyl, dicarboxymethallyl and mixed carboxyallyl carboxymethallyl esters of phenyl indan are novel compositions of matter. These compounds [52] 260/313 2 are useful as crosslinking and plasticizing agents for 51 im. Cl. C08f 45/36, C08g 51/34 plymem compmmons [58] Field of Search 260/475 R, 3 1.8 F, 785 BB, 8 Claims, N0 Drawings This invention relates to novel esters of phenyl indan having the structural formula:

s te- H; C CH3 wherein A, B, C, DYE and i are saaaea from in;

group consisting of hydrogen, carboxyallyl and carboxymethallyl radicals; and wherein one of A, B and C and one of D, E and F is a carboxyallyl or a carboxymethallyl radical.

As illustrative of particularly preferred compounds of this invention are those having the structural formula:-

wherein R1 and R2 p iy' aaarraafhe group consisting of hydrogen and methyl radicals.

We have found that these compounds possess excellent properties as plasticizing and as crosslinking agents for a variety of polymeric compositions and particularly for high temperature processing fluorocarbon homopolymers and copolymers such as ethylene-tetrafluoroethylene copolymers, ethylene-chlorotrifluoroethylene copolymers, polyvinylidene fluoride homopolymers, tetrafluoroethylene-vinylidene fluoride copolymers, tetrafluoroethy]enehexafluoropropylene copolymers, vinylidene flouride-hexafluoropropylene copolymers, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymers and the like. The new compounds have been found to be particularly useful as crosslinking coreactants which assist in providing elevated temperature deformation resistance in the crosslinked product. The compounds also exhibit very useful plasticizing properties during processing of the polymeric compositions.

Our new compounds can be produced by reacting a precursor phenyl indan dicarboxylic acid such as a 1,1,-

3-trimethyl-5-carboxy-3-(p-carboxyphenyl) indan diacid with thionyl chloride to produce the corresponding diacyl chloride and reacting this diacyl chloride with allyl alcohol, methallyl alcohol or a mixture of allyl and methallyl alcohol. The precursor diacid starting materials are already known and are produced from a suitable tetramethyl-3-tolyl indan by a catalytic air oxidation process similar to that described in an article by P. Towlc and H. Baldwin in Hydrocarbon Processing 43(11) 149(1964).

Alternatively, these new compounds can be prepared by other methods including direct esterification, catalyzed esterification or interchange esterification from saturated esters. Additionally, the compounds can be produced from a phenyl indan dinitrile or dialdehyde or like intermediates by known techniques.

As illustrative of the preparation of the compounds of this invention are the following:

EXAMPLE 1 'To a suitable reaction vessel equipped with a thermometer and reflux condenser was charged grams (0.19 mole) of 1,1,3-trimethyl-5-carboxy-3-(pcarboxyphenyl) indan and 74 grams (0.62 mole) of thionyl chloride. The so charged mass was heated carefully until solution occurred and then refluxed overnight. Excess thionyl chloride was distilled, first at atmospheric pressure and finally at the aspirator. Then, 66 grams (1.14 moles) of allyl alcohol were added and the reaction mixture was heated overnight under reflux. Most of the excess allyl alcohol was stripped and the residual molten mass slurried several times with dilute sodium carbonate solution and finally with water. After collection and air drying on a Buchner funnel, the resulting powdered cake was oven dried for one hour at C to obtain 73 grams (58 percent of the theoretical) of a buff colored powder melting at 8284 C. The resulting product was then recrystallized from ethanol to yield a lighter buff colored product which was characterized by infrared spectroscopy as the diallyl ester of l,l,3trimethyl- 5-carboxy-3(p-carboxyphenyl) indan, M.P. 84 C(at a 5 C/minute differential scanning calorimeter rate).

EXAMPLE II Employing the procedure of Example I, 50 grams (0.155 mole) of 1,1,3-trimethyl- 5-carboxy-3-(p-carboxyphenyl) indan and 50 ml. (0.68 mole) of thionyl chloride were refluxed with exclusion of atmospheric moisture for 8 hours. Excess thionyl chloride was removed at atmospheric pressure and finally under aspirator vacuum. Thirty-five ml. (0.71 mole) of methallyl alcohol were added to the resultingdiacyl chloride and after reflux for 2 hours the mixture was poured into water and subsequently washed successively with'dilute aqueous sodium carbonate and water. The mixture was then distilled under reduced pressure and 40 grams of a deep strap colored product were collected at 245-6 C/O.7 Torr. The product was cooled to produce a viscous liquid which-was not ra 1iLY..sry t i bl The PF QQQE;h? l1? I 9 by infrared spectroscopy as the dimethallyl ester of 1,1,3-trimethy1-5-carboxy-3-(p-carboxyphenyl).;indan.

EXAMPLE lll Employing the procedure of Example I, 50 grams of 1 ,1 ,3-trimethyl-5-carboxy-3-(p-carboxyphenyl) indan and 50 grams of thionyl chloride were reacted and the resulting reaction product was treated with a mixture of 24 grams (0.35 mole) of methallyl alcohol and 20 grams (0.35 mole) of allyl alcohol. Isolation by the method of Example ll, yielded 38 grams (58.5% yield) of a straw colored liquid which boiled at 23845 C/O.7 Torr. 1

Examination of the resulting product in carbon tetrachloride solution by nuclear magnetic resonance spectroscopy showed the presence of essentially equimolar quantities of allylic and methallylic groups indicating that the product was a mixed allyl-methallyl diester of 1,1 ,3-trimethyl-5-carboxy-3-(p-carboxyphenyl )indan.

The compounds of this invention have been found to possess particularly useful characteristics as additives to accelerate the crosslinking of polymers by chemical or irradiation activation. Thermal testing has shown that these compounds have very excellent thermal stability and very low volatility when compared with the acrylic, methacrylic and allylic compounds employed heretofore as crosslinking accelerators. Furthermore, the present compounds possess solubility or plasticizing properties which render them compatible with a variety of polymeric systems. For example, ethylenetetrafluoroethylene copolymers and ethylene-chlorotrifloroethylene copolymers are known to exhibit unusually high chemical resistance and tend to reject plasticizer or solvent which is incorporated therein. However, we have discovered that the esters of the present invention are quite compatible with these fluorinated copolymers which is surprising in view of previously reported data indicating that these copolymers have high resistance to solvation and swelling. In fact, we have found that by incorporation, for example, the diallyl esters of the present invention into these copolymers, extrusion thereof is achieved at considerably lower temperature profiles. In accordance with this finding, the following table is set forth to illustrate the decrease in torque achieved by the incorporating of the diallyl ester of l ,1 ,3-trimethyl--carboxy-3-(p-carboxyphenyl) peratures, for example, to provide continuous thin wall extrusions or at equivalent temperatures can provide substantially thinner walled extrusions as compared with compositions containing the prior art trially cyan- 5 urate crosslinkers.

As illustrative of the excellent mechanical and aging properties possessed by crosslinked polymeric compositions containing the compounds of the present invention, are the following:

EXAMPLE IV A polymeric composition was prepared by powder blending an ethylene-chlorotrifluoroethylene copolymer with 3% (by weight) of a diallyl ester of 1,1,3-

trimethyl-5-carboxy-3-(p-carboxyphenyl) indan proindan into various polymeric compositions as com- Tensile Strength 6387 psi pared with torque values achieved with no additive or '9"???" 10 ""l I 250 with the addition of a standard prior art crosslinking F m 339 I ensl e reng psi coreactant compound (|.e., triallyl cyanurate)m the Elongation (at IOU/minute Stretch) 263% polymeric compositions: Hot Modulus 43 7 TABLE I MONOMER INCORPORATED IN WEIGHT MIXING TORQUE CHAMBER POLYMERIC THE POLYMERIC OF TEMPERATURE (METER- MONOMER V COMPOSITION COMPOSITION (F) GRAMS) Ethylene-tetrafluoro- None 580 900 ethylene copolymer 7 do. D iallylester gfbl, v 580 800 3-trimethyl-3-(p-5 i I' carboxyphenyl) indan do. Triallyl cyanurate 5 580 l 100 Ethylene-chlorotri- None 500 1660 fluoroethylene copolymers do. Diallyl ester of l ,l .3- 5 500 1450 trimcthyl-3-(p-5 carboxyphenyl) indan do. Triallyl cyanurate 5 500 1660 Polyvinylidene fluoride None 550 1950 homopolymer do. Diallyl ester of 1,] ,3- 5 550 1650 trimethyl-3-(p-5 carboxyphenyl) indan do. Triallylc yanurate 5 550 1950 These experiments were conducted in a Brabender" sigma type mixer using a gram total charge in each case employing the noted temperatures at a shear rate of rpm. It should be iibifirdm the tabulated data that duev to the compatability of the diallyl ester of the present,

invention in the polymeric compositions, a substantial decrease in torque is exhibited whereas the noncompatible prior art trially] cyanurate additive does not provide this effect.

This reduction in torque values indicates that the polymeric compositions containing the diallyl ester of thepresent invention can be processed at lower temmegarad dose were aged at 200 C and tested for tensile strength and elongation after cooling to room temperature (about 25C.). The results of this testing demonstrating the superior aging qualities possessed by Additionally, the irradiation crosslinked compositions were tested for aging characteristics by the procedure of Example V. The results of this testing were as follows:

polymeric composition containing a diallyl ester of the present invention were as follows:

To show the effectiveness of crosslinked polymeric compositions containing a plasticizing and crosslinking TABLE I1 MONOMER INCOR- PORATED INTO ETHYLENE- IRRADIATION CHLQROTRIFLUOROETHYLENE DOSAGE AGING PERIOD (HRS.) COPOLYMER (MEGARADS) TEST 24 72 168 None 10 Tensile Strength 635] 5305 4515 4163 (psi) Diallyl ester of 1,1,3-trimethyl- 10 do. 6387 5447 g 5494 5593 -carboxy-3-(p-carboxyphenyl) indan None Elongation at 350 342 396 329 10 inches-per minute stretch Diallyl ester of 1,1.3-trimethyl- 10 250 I 242 233 221 5-carboxy-3-(p-carboxyphenyl) indan EXAMPLE VI A polymeric composition was prepared by sheeting out a vinylidene fluoridehexafluoropropylene copolymer on a two-roll unheated mill and milling 4% (by weight) of a diallyl ester of 1,1,3-trimethyl-5-carboxy- 3-(p-carboxyphenyl) indan and 1% (by weight) magnesium oxide into the copolymer. The sheet was removed from the mill and sliced into small sections. The resulting sections were compression molded at 475 F between Ferrotype plates with a 6 square inch shim cavity tively,

therein to produce several 35 mil slabs. These slabs were irradiated at 5 and 10 megarads doses in a 1.5 MEV electron beam accelerator to produce crosslinked polymeric compositions having the following mechanical properties at room temperature (about 25 C) and at elevated temperature (250 C):

agent of the present invention for use as insulations for wires, the following example is set forth:

EXAMPLE VlI A sample comprising pure ethylene-tetrafluoroethylene copolymer and two additional samples comprising ethylene-tetrafluoroethylene copolymer and 3.5 percent (by weight) and 5.0 percent (by weight), respecof diallyl 1,1 ,3-trimethyl-5-carboxy-3-( pcarboxyphenyl) indan were prepared by a powder blending process similar to that shown in Example IV. The resulting three sample compositions in powdered form, were then extruded'through an extruder having a head temperature of 530 F. to form rods. The rods were then pelletized and the 'pellets were extruded onto the surface of a 20 gauge tin coated copper wire. The 3. Th-epoly nieric"compositionof claim 6 'wherein extrusion conditions for the wire insulation were as folsaid composition contains a high temperature processlows: ing fluorocarbon homopolymer or copolymer. LERGMERTREDRTDRAED m lNTO ETHYLENE- TEMPERATURES (F) TETRAFLUOROETHYLENE WEIGHT BARREL ZONES DIE HEAD COPOLYMER l 2 3 None 580 600 600 670 710 Diallyl ester of 1,1 ,3-trimethyl- 3.5 560 560 560 600 650 -5-carboxy-3-(p-carboxyphenyl) indan The three insulated wires were then subjectedtoha 1. lhe polymefic composition of claim 3 wherein diation with high energy electrons by a 1.0 MEV resosaid fluorocarbon homopolymer or copolymer is senant beam transformer. The resulting Insulated wires lected from the group consisting of ethylene-tetrawith irradiation crosslinked coatings were then anfluoroethylene copolymers, ethylene-chlorotrifluoronealed and subsequently tested to determine their me- 7 ethylene copolymers, polyvinylidene fluoride homopolchamcal and electrical properties. The results of this ymers, tetrafluoroethylene-vmylldene fluoride copolytestmg are set forth In the following table: mers, tetrafluoroethylene-hexafluoropropylene copoly- ETHYLENE- ETHYLENE- TETRAFLOUROETHY- TETRAFLUOR- 'ETHYLENE- LENE OETHYLENE mm 3.5% (BY WEIGHT) WITH 5.0% (BY WEIGHT) ,TETRAFLUOR- OETHYLENE DlALLYL ESTER DIALLYLESTER (N0 ADDlTlVES) l0 Megarad l5 Megarad l0 Megarad l5 Megarad 1O Megarad l5 Megarad TESTS Dose Dose Dose Dose Dose Dose Insulation Weight (lbs/l000ft.) 3.0 2.9 3.0 2.98 3.0 3.0 Tensile Strength 1 (psi room temp.) 7832 6711 6198 6287 5229 5562 Elongation (room temp.) (at l0"/minute stretch) 158 I08 100 100 I33 200 Solder lron (seconds) 300 300 300 300 26.6 300 Mandrel Deformation (96 hrs., 250 C., a 2.5 lbs. load) Pass Pass Pass Pass I Refused Refused Voltage v Voltage Failed Failed 7 Tensile Strength (Psi of 275 c.) 109 1-17 I 104 10s 27 a 50 Elongation I (at 275 c.) 244 124 95 I 79 375 30 Hot Modulus (275 c., '50 psi) 48 45 34 Failed 29s ORKS 1 "1551i; mainaibh'sand5555661353? the Thers', vir'iylidfie ntiarrde heraflui pibii iene copolyinvention as hereinbefore set forth may be made withmers, and vinylidene fluoridehexafluoropropyleneout departing from the spirit and scope thereof, theretetrafluoropropylene copolymers.

fore, only such limitations should be imposed as are in- 4 5. A c rosslinkded polymeric composition containing dicated in the appended claims. an ester of phenyl indan having'the structural formula:

We claim: 1. A' polymeric composition having incorporated. a A c therein a plasticizing and crosslinking agent comprising 50 B an ester of phenyl indan having the structural formula: E

. A Q C I B l k E v .HaC CH3 v Q C i wherein A, B, C, D, E and F are selected Famine group consisting of hydrogen, carboxyallyl, and carmo CH; boxymethallyl radicals; and wherein one of A, B and C h I d g A W v and one ofD,.E andFisacarboxyallyloracarboxyme wherein A, B, C, D, E and F are selected from the thallyl radical.

group consisting of hydrogen, carboxyallyl, and car-' 6. The crosslinked polymeric composition of claim 5 boxymethallyl radicals; and wherein one of A, B and C wherein said ester of phenyl consisting of the diallyl and'one of D, E and F is a carboxyallyl or a'carboxymeester of 1,1,3-trimethyl-5-carboxy-3-(pthallyl radical. carboxyphenyl) indan, dimethallyl ester of 1,1,3-

' 2. The polymeric composition-of claim 1. wherein the trimethyl-5-carboxy-3.-(p-carboxyphenyl) indan mixed plasticizing and crosslinking agent is selected from the allylmethallyl, diesterof 1,1,3-trimethyl-5-carboxy-3- group consisting of the diallyl esterof 1,1,3-trimethyl- (p-carbo ryphenyl) indan and mixturesthereof.

5-carb'oxy-3-(p carboxyphenyl) indan,- diamethallyl .7. The, crosslinked polymeric composition of claim 5. ester I I of l,1,3 trimethyl-5-carboiry-3-(pwherein said composition contains a high temperature carboxyphenyl) indan, and mixtures thereof. 3 processing fluorocarbon homopolymer or copolymer.

mers, t e trafluoroethylenehekafluoropropylene copolymers and vinylidene fluoride-hexafluoropropylene cofluoridecopolypolymers, and vinylidene hexafluoropropylene-tetrafluoropropylene mers. 

1. A POLYMERIC COMPOSITION HAVING INCORPORATED THEREIN A PLASTICIZING AND CROSSLINKING AGENT COMPRISING AN ESTER OF PHENYL INDAN HAVING THE STRUCTURAL FORMULA:
 2. The polymeric composition of claim 1 wherein the plasticizing and crosslinking agent is selected from the group consisting of the diallyl ester of 1,1,3-trimethyl-5-carboxy-3-(p-carboxyphenyl) indan, diamethallyl ester of 1,1,3-trimethyl-5-carboxy-3-(p-carboxyphenyl) indan, and mixtures thereof.
 3. The polymeric composition of claim 6 wherein said composition contains a high temperature processing fluorocarbon homopolymer or copolymer.
 4. The polymeric composition of claim 3 wherein said fluorocarbon homopolymer or copolymer is selected from the group consisting of ethylene-tetrafluoroethylene copolymers, ethylene-chlorotrifluoroethylene copolymers, polyvinylidene fluoride homopolymers, tetrafluoroethylene-vinylidene fluoride copolymers, tetrafluoroethylene-hexafluoropropylene copolymers, vinylidene fluoride-hexafluoropropylene copolymers, and vinylidene fluoridehexafluoropropylene-tetrafluoropropylene copolymers.
 5. A crosslinkded polymeric composition containing an ester of phenyl indan having the structural formula:
 6. The crosslinked polymeric composition of claim 5 wherein said ester of phenyl consisting of the diallyl ester of 1,1,3-trimethyl-5-carboxy-3-(p-carboxyphenyl) indan, dimethallyl ester of 1,1,3-trimethyl-5-carboxy-3-(p-carboxyphenyl) indan mixed allylmethallyl diester of 1,1,3-trimethyl-5-carboxy-3-(p-carboxyphenyl) indan and mixtures thereof.
 7. The crosslinked polymeric composition of claim 5 wherein said composition contains a high temperature processing fluorocarbon homopolymer or copolymer.
 8. The crosslinked polymeric composition of claim 7 wherein said fluorocarbon homopolymer or copolymer is selected from the group consisting of ethylene-tetrafluoroethylene copolymers, ethylene-chlorotrifluoroethylene copolymers, polyvinylidene fluoride homopolymers, tetrafluoroethylene-vinylidene fluoride copolymers, tetrafluoroethylenehexafluoropropylene copolymers and vinylidene fluoride-hexafluoropropylene copolymers, and vinylidene fluoride-hexafluoropropylene-tetrafluoropropylene copolymers. 